Coloring matters of the phthalocyanine series



Patented June 13, 1944 ooroamc MATTERS or THE rn'ruano- UYANINE scams Norman Hulton Haddock, Blackley, Manchester,

England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application July 15, 1942, Serial No. 451,075. In Great Britain June 6, 1939 11 Claims.

This application is a continuation-in-part of my copending application, Serial No. 335,872, filed May 1'7, 1940.

This invention relates to new coloring matters of the phthalocyanine series. More particularly, this invention deals with primary polyazo compounds of the phthalocyanine series, useful as direct dyestufis for cotton and further useful for conversion into pigments.

In an earlier application of. mine, Serial No. 335,871, filed May 17, 1940 (now Patent, No. 2,280,072, issued April 21, 1942) I'have described a novel method for producing metal-free and metallic tetra-amino-phthalocyanines, obtained by reduction of the corresponding tetranitrophthalocyanines. 1

As typical tetranitro-phthalocyanines whic may be economically employed for this purpose,

there were mentioned copper-tetra-(4) -nitrophtha-locyanine, copper-tetra- (3) -nitro-phthalocyanine, mixtures of these; other metallic tetranitro-phthalocyanines for instance those of cobait, nickel, aluminum, lead or magnesium; and also metal-free tetranitro-phthalocyanine.

The tetra-amines thus obtained were described as generally green in color and insoluble in water. They are turned blue by the action of acids, for example hydrochloric acid, seemingly owing to salt formation. When subjected to the action of nitrous acid, they are readily diazotized, and in this form are useful as intermediates, namely diazo components, in the preparation of coloring matters.

In a similar manner, phthalocyanines having three or two diazonium groups may be prepared by starting with the corresponding trinitro and dinitro-phthalocyanines. These in turn may be prepared by synthesizing phthalocyanines from the preferred metal, say copper or cobalt, on the one hand and from a mixture of phthalonitrile and nitrophthalonitrile (in molal ratio 1:3 or 2:2, respectively) on the other hand.

, Also, by starting with a tetranitro-phthalocyanine and reducing to a tetra-amino compound but using then a limited quantity of nitrous acid, phthalocyanine compounds containing less than four diazo groups per molecule may be produced.

Now, according to my present invention, the above tetra-, trior di-didiazo-phthalocyanine compounds, hereinafter referred to generically as polydiazo-phthalocyanines, may be converted into valuable dyestuffs by coupling the same to coupling components containing water-solubilizing groups, such as sulfo or carboxy.

. As suitable polydiazo-phthalocyanine compounds, any of those specifically mentioned above may be employed, as well as numerous other polydiazo-phthalocyanine compounds of the benzene series.

As coupling components suitable for the purpose of this invention come into consideration the various naphthol-sulfonlc acids, aminonaphthol-sulfonic acids, aryl-pyrazolone-carboxylic acids, sulfo-aryl-pyrazolones, and the various substitution products of the aminonaphthol-sulfonic acids which are still capable of coupling, as for example acylamino-naphtholsulfonic acids. As further specific examples of these, by way of illustration, the following may be named:

l-naphthol-4-sulphonic acid (Nevile and Winther) l-naphthol-B-sulphonic acid (L acid) 1 -naphthol- 3 fi-disulphonic acid 1-naphthol-3 :6 8-trisulphonic acid 2-naphthol-6-su1phonic acid (Schaefler) 2-naphthol-3 fi-disulphonic acid (R. acid) 2-naphthol-6:B-disulphonic acid (G acid) 1 8-dihydroxynaphthalene-3 G-disulphonic acid (Chromotrope) 1-amino-8-naphthol-4-sulphonic acid (S acid) l-amino-8-naphthol-3tfi-disulphonic a c i d (H acid) 2-amino-5-naphthol-7-sulphonic acid (J acid) 2-amino-8-naphthol-6-su1phonic acid (gamma acid) 1-m-sulfophenyl-3-methyl-5-pyrazolone l-acetylamino-8-naphthol-3,6-disulfonic acid As the coupling involves a reaction between one molecule of a tetradiazo-compound and as high as four molecules of coupling component, it is possible to use as coupling components the naphtholor amino-naphthol-sulphonic acids in various ways; that is, diflerent coupling components may be mixed in a variety of proportions, or the coupling may be caused to take place by stages, with diiferent coupling components.

The dyestufis of the invention, extending on his principles the classification of Winther, Patente der organischen Chemie, Giessen, 1908 vol. II, Table, may be termed wholly primary tetrakisa-zo dyestufis. However, quantitative coupling determinations have shown that the coupling often does not go to completion. Apparently, some of the diazo groups undergo decomposition during the coupling step, with the result that the final dyestufi is a mixture of primary disazo, trisazo and tetrakisazo compounds.

The compounds of this invention may therefore be expressed by the general formula Q(N=N-A), wherein Q is the radical of a phthalocyanine compound of the benzene series, A is an azo coupling component containing water-solubilizing groups, while a: is an integer not greater than 4, and more commonly probably 2 to 4.

The coupling is carried out in alkaline or neutral medium; and in the case of the aminonaphthol sulphonic acids, also in acid medium.

Phthalocyanines not substituted in the outer rings are intensely colored, usually blue, but as substituents are introduced into the outer rings the shade tends to become greener and may become quite green. It was not to be expected that the products of the present invention would have technically valuable violet, brown and blue shades.

Furthermore, the products of the invention have been found to possess direct afflnity for cotton and regenerated cellulose.

The novel compounds may also be converted into lakes, by treatment for instance with barium chloride or other agents generally employed for the laking of dyestuffs containing sulfo or carboxy groups.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1 30 parts of copper tetra-(4)-aminonaphthalocynanine are stirred with parts of sodium nitrite and 500 parts of water. To this mixture are quickly added 500 parts of 33% aqueous hydrochloric acid at below 8 C. After a few minutes stirring a clear deep green dlazo solution is obtained. This tetra-diazo solution is gradually added to 76 parts of 1-naphthol-3z6z8- trisulphonic acid dissolved in 1000 parts of water. During the addition the mixture is kept alkaline by adding sodium carbonate solution as needed. When coupling is complete the solution is heated and sufficient common salt is added to precipitate the dyestuff. It is filtered off, washed with 5% aqueous solution of common salt, dried and pulverised. The product is a dark powder, soluble in water to give a reddish-violet solution from which cotton is dyed at the boil in violet shades.

Other combinations prepared in similar manner to Example 1 are shown in the following table:

. Shade of the Coupling component (4 molecular Example proportions) K883312153 fazo 2 2-naphthol-fiz 'disulphonie acid Dark-blue.

3 2-naphth0l-3:6-disulphonic acid Red-violet.

4 Z-naphthol-Bsulphonic acid D0.

6 2-amino-5-naphthol-7-sulphonic acid. Do.

6 1: 8 4 dihydroxynaphthalene 3: 6 di- Violet.

sulphonic acid.

Example 7 of sodium carbonate as needed and the temperature is kept below 5 C. When coupling is complete the solution is heated and suiilcient common salt added to precipitate the dyestuii". It is filtered off, washed with 20% aqueous solution of common salt, dried and pulverised. The product is a dark powder, soluble in water to give a reddish-violet solution from which cotton is dyed at the boil in violet shades. It is believed to be a mixture of the tetrakisazo, trisazo and disazo derivatives of copper phthalocyanine and the named coupling component.

Other combinations prepared in a similar manner to Example 7 are shown in the following table:

Example 13 Cobalt-tetra-4-amino-phthalocyanine (2 grams in the form of a 10% paste) is pasted with 26.5 parts of 10 normal hydrochloric acid and is then azotized at about 10 C. with 13 parts of 10% sodium nitrite. This solution is then added to a solution at 5 C. of 1-acetyl-amino-8-naphthol- 3,6-disulf0nic acid (7.2 parts) in the presence of suilicient sodium carbonate to maintain distinct alkalinity on brilliant yellow papers at all times. This product dyes cotton in violet shades.

In a similar manner, copper-tetra-3-amin0- phthalocyanine and metal-free-tetra-4-aminophthalocyanine have been azotized and coupled under alkaline conditions with oxy-Koch acid (1-naphthol-3,6,8-trisulfonic) and acetyl-H acid (l-acetcylamino-8-naphth0l-3,6-disulfonic) The shades obtained were similar to those obtained from copper-tetra-4-amino-phthalocyanine with the same coupling components.

As already indicated, the above dyestuffs may be readily converted into lakes by treatment with barium chloride or similar agents. The following additional examples illustrate this phase of the invention.

Example 14 166.3 parts of the dyestuif obtained by tetradiazotizing copper tetra 4 amino-phthalocyanine and coupling to 4 moles of l-naphthol- 4-sulfonic acid (as the sodium salt) are dissolved in water. To this dye solution there is added an aqueous solution of 62.4 parts of barium chloride in 650 parts of water. The product precipitates out in the form of its barium lake, is filtered oil, and dried. These pigments may be formed in the presence of a white pigment such as aluminum hydrate or barium sulfate. The shade of such a product, when dispersed in a vehicle and applied to a card, gives a very dull violet shade with good light fastness.

In place of barium chloride as the laking metal, other water-soluble barium salts may be used. In place of barium salts, water-soluble calcium or strontium salts may be substituted.

In the following table are shown the shades obtained in similar manner from various other phthalocyanine-azo dyes, using barium salts as Shade of dis- Coupling component (4 molecular Exampii proportion!) persegslalke on 15 2-naphthol-3,6-dlsulionic acid Dull-violet. 1o 1,B-dihydroxy-naphthalene-3,ii-dlsul- Blue-grey. ionic acid. l7 2-naphthol-6,8-disulionlc acid Grey. 18 l-naphthl-3,6.8-trisulionic acid Dul -purpic. l9 i-acetyiamlno-S- naphthol-3 ,o-disul- Blue-violet.

, ionic acid. 20 1 oluenesulionylamino 8- naph- Dull-violet.

t oi-3,o-disuilonlc acid. 21 3"- (g-hydroxy-ethyl) -amlnnnaph- Dull blue-green. t ol-l-sulionic acid.

The column of shades in the above table gives the shades obtained in each case by diluting the lake with a standard proportion of white pigment, dispersing in a vehicle and smoothing out on a white card as is customary ior shade and light-fastness determination.

As many apparently widely dlflerent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to specific embodiments except as defined in the appended claims.

I claim:

1. A water-soluble dyestufi consisting of a phthalocyanine molecule coupled by azo bridges onto azo-coupling components selected from the group consisting acids, the amino-naphthol sulfonic acids, the aryl-pyrazolone-carboxylic acids, the sulfo-arylpyrazolones and the N-substituted amino-naphthol-suiionic acids.

2. A dyestufl oi the general formula Q-(N=N--A) I wherein Q is the radical of a phthalocyanine compound of the benzene series, A is an azo coupling component selected from the group consisting of the naphthol-sulionic acids, the aminonaphthol sulionic acids,the aryl-pyrazolone-carboxylic acids, the sulio -aryl-pyrazolones and the N-substituted amino-naphthol-sulionic acids while a: is an integer not less than 2 and not greater than 4.

3. A water-soluble derivative of copperphthalocyanine consisting of a copperphthalocyanine molecule coupled by azo bridges to azocoupling components selected from the group consisting of the naphthol-sulionic acids. the amino-naphthol sulfonic acids, the aryl-pyrazolone-carboxylic acids, the suiio-aryi-pyrazolones and the N-substituted amino-naphtholsulionic acids.

of the naphthol-sulfonic 4. A dyestufl oi the general formula (CuPc)-(N=N-A)= wherein CuPc designates the radical of copperphthalocyanine, A is an azo coupling component selected from the group consisting of the naphthol-sulionic acids, the amino-naphthol sulfonic acids, the aryl-pyrazolone-carboxyllc acids, the

' sulfo-aryl-pyrazolones and the N-substituted amino-naphthol-sulfonic acids while a: is an integer not less than 2 and not greater than 4.

5. The water-soluble am dyestufis obtainable by a process comprising coupling water-soluble tetra-diazotized ,tetraaminophthalocyanines of the benzene series with azo coupling components selected from the group consisting of the naphthol-sulfonic acids, the amino-naphthol sulionic acids, the aryl-pyrazolone-carboxylic acids, the sulfo-aryl-pyrazolones and the N-substituted amino-naphthol-sulionic acids.

6. The water-soluble azo dyestuffs obtainable by a process comprising coupling tetra-diazotized copper tetra-(4) -amino-phthalocyanine with four moles of an azo coupling component selected from the group consisting of the naphthol-sulionic acids, the amlno-naphthol sulfonic acids, the aryl-pyrazolone-carboxylic acids, the sulfo-aryl-pyrazolones and the N-substituted amino-naphthol-sulfonic acids.

7. Process for the manufacture of water-soluble azo dyestuffs comprising coupling watersoluble tetra-diazotized cyanines of the benzene series with azo coupling components selected from the group consisting of the naphthol-sulfonic acids, the aminonaphthol-sulionic acids, the aryl-pyrazolonecarboxylic acids, the sulfo-aryl-pyrazalones and the N-substituted amino-naphthol-sulfonic acids.

8. A process for the manufacture of water- -amino-naphthol-sulfonic acids.

9. The water-insoluble alkaline-earth metalsalts of the dyestuffs defined by claim 2.

10. The barium lake of a dyestufi as defined in claim 5.

11. The barium lake of a dyestufi as defined in claim 6.

NORMAN HULTON HADDOCK.

- tetra-aminophthalo- CERTIFICATE OF CORRECTION.

Patent No. 2,551,118. June 15, 191m.

NORMAN HULION EADDOGK.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follews Page 1, first column, line 14.9, for "di-didiazo" read --di*-diazo--; and that the said Letters Patent should be read wi'th this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed. this 29th day of August, A. D. 191 1;.

Leslie Frazer (Seal) Acting Commissioner of Patents. 

